【発明の詳細な説明】［産業上の利用分野］本発明は、不伝導基質」二の銀の沈着、さらに具体的に
は、その層が非常に薄い層の沈着に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the deposition of silver on nonconductive substrates, and more particularly to the deposition of very thin layers thereof.
［従来の技術および発明が解決しようとする課題］不伝
導基質上のある種の金属の薄層は非常に重要な商業的利
用性価値がある。透明基質上の伝導金属の薄層は電子表
示装置に利用し得る。薄層は太陽光線の遮光、その他の
ソーラー装置において、熱を反射し、太陽光線の放射を
ろ過するために使用される。薄層は、人体への挿入前に
薄層で器具を被覆すれば、人体に挿入する器具により惹
起される感染の範囲を減少させ得る。薄層は防湿塗装と
して、包装に使用し得る。これらの使用例は薄層の何千
もの用途のほんの一例にすぎず、なんらその用途を制限
するものでない。BACKGROUND OF THE INVENTION Thin layers of certain metals on nonconducting substrates are of very important commercial utility value. Thin layers of conductive metals on transparent substrates can be used in electronic displays. Thin layers are used in solar shading and other solar devices to reflect heat and filter solar radiation. A thin layer can reduce the extent of infection caused by a device inserted into the human body if the device is coated with a thin layer prior to insertion into the human body. The thin layer can be used in packaging as a moisture barrier coating. These examples of uses are just a few of the thousands of uses for the thin layer and are not intended to limit its use in any way.
ある具体例において、銀または銀含有化合物の薄層は、
特に人体中の微生物感染の抑制に効果的である。アメリ
カ合衆国特許第４４０４１９７号は火傷患者の感染のお
それを減少させるのに銀含有化合物の使用を開示してい
る。アメリカ合衆国特許第４６０３１５２号は抗感染の
ための銀化合物を利用した他の同様の機器を開示してい
る。アメリカ合衆国特許第４０５４１９９号および第４
４８３６８８号は感染範囲の減少のために医療機器に純
銀コーティングの利用を開示している。すなわち、銀ま
た銀化合物のコーティングは体内に移植また挿入する医
療機器による感染の機会を減少さ仕るのに効果的である
ことが立証されている。In certain embodiments, the thin layer of silver or silver-containing compound is
It is particularly effective in suppressing microbial infections in the human body. US Pat. No. 4,404,197 discloses the use of silver-containing compounds to reduce the risk of infection in burn patients. U.S. Pat. No. 4,603,152 discloses another similar device utilizing silver compounds for anti-infective purposes. U.S. Patent Nos. 4,054,199 and 4
No. 483,688 discloses the use of pure silver coatings on medical devices to reduce the extent of infection. Thus, silver or silver compound coatings have proven effective in reducing the chance of infection from medical devices implanted or inserted into the body.
感染を防止するための銀の使用は十分に立証されている
が、表面に銀を塗装する方法の効果的な操作に関しては
ほとんど知られていない。電着電気メツキを利用しても
よいが、多くの場合、医療機器は不伝導材料で製造され
ており、容易に商業的規模で薄層付着被覆層をコーティ
ングすることができない。特許第４０５４１３９号は化
学メツキにより沈着させるタイプのコーティングが可能
であることを示唆しているが操作方法の詳細な説明はな
い。特許第４４８３６８８号はカテーテルの被覆に３０
０メソンユの大きな粒子の銀の使用を記載している。Although the use of silver to prevent infection is well documented, little is known regarding the effective operation of methods for coating silver on surfaces. Although electrodeposition electroplating may be utilized, medical devices are often made of non-conductive materials and cannot easily be coated with thin deposit coatings on a commercial scale. Patent No. 4,054,139 suggests that a type of coating deposited by chemical plating is possible, but does not provide a detailed explanation of the method of operation. Patent No. 4,483,688 covers 30% of catheter coatings.
The use of large grain silver of 0 mesonyu is described.
銀は化学的方法により不伝導基質上にコーティングする
ことが可能である。−例をあげると、鏡−Ｈの銀コーテ
イングに使用する方法であるが、このコーティングは比
較的層の厚いものである。他の例は蒸着またはスパッタ
ーのような乾式沈着技術であるが、これらは不揃いの形
の基質や、深い空洞にコーティングすることができない
。Silver can be coated onto nonconducting substrates by chemical methods. - For example, the method used for the silver coating of Mirror-H, which is a relatively thick coating. Other examples are dry deposition techniques such as evaporation or sputtering, but these cannot coat irregularly shaped substrates or deep cavities.
銀は環境によっては毒性を有し、高価であるから、電気
的に不伝導な基質に非常に薄い層で銀をコーティングす
ることが好ましい。コーティングの欠損は、感染や体内
を銀が通過を惹起する可能性があるため、コーティング
層は基質に強固に付着していなければならない。現在の
ところ、非常に薄いしかも均一で透明な層で、ｌ−２０
００オングストロームのオーダーの厚さで沈着を可能に
し、良好な機械的性質を持った強固な付着層を形成し、
被覆物質の大規模商業的製造に容易に適用し得る種々の
形の不伝導基質に銀を沈着させる技術は公知でない。Since silver is toxic in some environments and expensive, it is preferred to coat the electrically non-conducting substrate with silver in a very thin layer. The coating layer must adhere strongly to the substrate, as defects in the coating can lead to infection and passage of silver into the body. At present, it is a very thin, uniform and transparent layer, l-20
It enables deposition at thicknesses on the order of 0.00 angstroms, forming strong adhesion layers with good mechanical properties,
There are no known techniques for depositing silver on various forms of nonconductive substrates that are readily amenable to large scale commercial production of coating materials.
従って、このようなコーティング技術か求められている
。本発明はこの要求を充たし、さらにこれに関連する利
益を提供するしのである。Therefore, such a coating technology is required. The present invention satisfies this need and provides further related benefits.
［発明の構成］本発明は広範な種類の不伝導基質上に銀の均一な薄層を
沈着させる方法に関する。銀層は密着しており、例えば
、抗菌性医療への利用、遮蔽塗装、および光学用フィル
ターなどの用途を含む種々の利用が可能である。本発明
は外界温度かまたはわずかに高い温度にて、通常の工業
的化学的操作法により行うことができる。本方法は、非
常に制御しやすく、再現性があり、種々の基質上に実質
的に均一な層を形成し得る。本発明の手段を使用してコ
ーティングされた高品質部分の形成率は非常に高い。SUMMARY OF THE INVENTION The present invention relates to a method for depositing uniform thin layers of silver on a wide variety of nonconducting substrates. The silver layer is adherent and has a variety of uses including, for example, antibacterial medical applications, barrier coatings, and optical filter applications. The invention can be carried out at ambient or slightly elevated temperatures using conventional industrial chemical procedures. The method is highly controllable, reproducible, and can form substantially uniform layers on a variety of substrates. The rate of formation of high quality parts coated using the means of the invention is very high.
本発明によれば、電気的に不伝導な基質の表面に銀の均
一な薄層を沈着させる方法は実質的に少なくとも約０．００１ｇ／ｌのスタンナスス
ズイオンの塩を含む活性化溶液中で表面を活性化するこ
と、銀含有塩、基質の表面に銀塩を還元して金属銀を生
成させ得るに十分な濃度の還元剤および溶液中の銀を析
出を防止し、基質の表面に銀の沈着を可能にするに十分
な濃度の沈着調整剤からなる沈着溶液から表面に銀を沈
着させること、沈着工程を暗所で行うことを含む。必要
ならば、基質の表面を処理前に洗浄することができる。In accordance with the present invention, a method for depositing a uniform thin layer of silver on the surface of an electrically nonconductive substrate is performed in an activating solution containing substantially at least about 0.001 g/l of a salt of stannous tin ions. activating the surface, containing a silver-containing salt, a reducing agent at a concentration sufficient to reduce the silver salt to the surface of the substrate to form metallic silver, and preventing silver in solution from precipitating and depositing silver on the surface of the substrate. depositing silver onto the surface from a deposition solution comprising a deposition control agent at a concentration sufficient to permit deposition of silver, and performing the deposition step in the dark. If necessary, the surface of the substrate can be cleaned before treatment.
銀層は沈着後で使用前に安定化させるのがよい。好適な
操作は、銀の均一な薄層を、好ましくは、沈着溶液中で
毎秒５−７オングストロームの割合で２−２０００オン
グストロームの厚さに沈着させる。表面層の厚さは容易
に調整し得る。得られた銀の層は不伝導基質に固着して
いる。他の特徴および利点を、下記のさらに具体的な実
施例の記載から明らかにするが、これは例示により、本
発明の詳細な説明するものである。The silver layer is preferably stabilized after deposition and before use. A preferred operation deposits a uniform thin layer of silver, preferably 2-2000 angstroms thick, at a rate of 5-7 angstroms per second in a deposition solution. The thickness of the surface layer can be easily adjusted. The resulting silver layer is adhered to a nonconductive substrate. Other features and advantages will become apparent from the description of more specific embodiments below, which serve as a detailed explanation of the invention by way of example.
［実施方法の説明］本発明のより優れた特徴によれば、電気的に不伝導基質
の表面上に銀薄層を沈着する方法であって、表面を水性
洗浄溶液中で洗浄すること、少なくとも約０．００１ｇ
／ｌのスタンナススズイオンを含む塩の水性活性化溶液
中で表面を活性化すること、ｐｔｔ値が約８以上であり
、硝酸銀、および基質の表面で銀塩を金属銀に還元する
に十分な濃度のホルムアルデヒド、硫酸ヒドラジン、水
酸化ヒドラジン、次リン酸からなる群から選ばれる還元
剤、溶液中の銀の析出を防止し、基質の表面に銀の沈着
を可能にするに十分な濃度の、転化糖、こはく酸、くえ
ん酸ナトリウム、酢酸ナトリウム、水酸化ナトリウム、
水酸化カリウム、およびアンモニアからなる群から選ば
れる沈着調整剤を含む沈着液から表面上に銀を沈着さ仕
ること（但し、暗所で沈着工程をおこなうものとする）
、白金族の金属の１種、金および白金族の金属の１種と
金の組み合わせからなる群から選ばれる金属の塩を少な
くとも約０．００１ｇ／ｌを希硝酸中に溶解し、得られ
た溶液のｐＨ値が約３０−約４．８である安定化溶液に
少なくとも約５秒間接触させて、コロイド状銀を沈着さ
せた表面に接触させて沈着銀を安定化させることを含む
。DESCRIPTION OF METHODS OF PERFORMANCE According to a further advantageous feature of the invention, there is provided a method for depositing a thin layer of silver on the surface of an electrically non-conducting substrate, the method comprising: cleaning the surface in an aqueous cleaning solution; Approximately 0.001g
activating the surface in an aqueous activating solution of a salt containing stannous tin ions/l, a PTT value of about 8 or greater, silver nitrate, and a sufficient amount of salt to reduce the silver salt to metallic silver at the surface of the substrate. a reducing agent selected from the group consisting of formaldehyde, hydrazine sulfate, hydrazine hydroxide, and hypophosphoric acid at a concentration sufficient to prevent precipitation of silver in the solution and to allow deposition of silver on the surface of the substrate; Invert sugar, succinic acid, sodium citrate, sodium acetate, sodium hydroxide,
Depositing silver onto a surface from a deposition solution containing a deposition control agent selected from the group consisting of potassium hydroxide and ammonia, provided that the deposition step is carried out in the dark.
obtained by dissolving at least about 0.001 g/l of a salt of a metal selected from the group consisting of a metal of the platinum group, gold, and a combination of a metal of the platinum group and gold in dilute nitric acid. contacting the colloidal silver-deposited surface with a stabilizing solution having a pH value of about 30 to about 4.8 for at least about 5 seconds to stabilize the deposited silver.
本発明は、種々の異なる不伝導基質材料の表面上にコロ
イド状金属銀を沈着させて行い得る。基質はそのもの自
体が伸縮性のフィルムか、剛性の固体であってもよい。The present invention can be practiced by depositing colloidal metallic silver on the surface of a variety of different nonconducting substrate materials. The substrate itself may be a stretchable film or a rigid solid.
例示であって、制限的ではないが、そのような材質には
ラテックス、ポリスチレン、ポリエステル、ポリ塩化ビ
ニル、ポリウレタン、ＡＢＳポリマー類、酸化アルミニ
ウムのようなセラミック、ガラス、ポリアミド、ポリカ
ーボネート、合成ゴムなどが含まれる。このような材質
の表面の性質は種々であるが、本発明の手段はこれらす
べてに適用可能である。By way of example and not limitation, such materials include latex, polystyrene, polyester, polyvinyl chloride, polyurethane, ABS polymers, ceramics such as aluminum oxide, glass, polyamide, polycarbonate, synthetic rubber, and the like. included. Although the surface properties of such materials vary, the means of the present invention is applicable to all of them.
基質の表面は、その後、活性化、沈着、および安定化溶
液でしめらすことができるように十分に清潔であること
が重要である。グリース、油、はこり、化学剤や、他の
物質による汚染層は、表面とこれらの溶液の反応性を阻
害するからである。It is important that the surface of the substrate is clean enough to allow subsequent soaking with activation, deposition, and stabilization solutions. Contaminant layers such as grease, oil, dirt, chemicals, and other substances inhibit the reactivity of these solutions with the surface.
湿潤が十分行なわれるように表面が最初に十分清潔であ
るならば、それ以後の洗浄は不要である。If the surface is initially clean enough for sufficient wetting, no further cleaning is necessary.
しかし、商業的利用における、多くの不伝導基質材料の
場合は表面が銀沈着前にほこりや有機物が全くないとは
言えないから洗浄が必要である。このような基質の表面
は好ましくは、不伝導基質に特有の適当な技術によって
洗浄されることが好ましい。 例えば、ボリカーポナー
ト、ポリアミド、ポリ塩化ビニル、ポリウレタン、およ
びポリエステル４０℃にて１０分間５％水酸化ナトリウ
ム溶液で洗浄する。ポリスチレンは３０−４０℃にて５
−２０分間ｌＯ％水酸化ナトリウム溶液で洗浄する。ラ
テックスおよび合成ゴムは室温にて１５分間３％次亜塩
素酸ナトリウム溶液中で洗浄する。酸化アルミニウムの
ようなセラミック類は、６０℃にて２０分間２０％硫酸
溶液中で、同時に少なくとも約５分間の超音波撹拌しつ
つ洗浄することができる。ポリイミドフィルムはアセト
ン中で洗浄することができる。ガラスは、ガラスに軽微
な食刻を与える０、５％フッ化水素酸および１０％硫酸
の水溶液中で洗浄することができる。ＡＢＳポリマーは
、６５−７０℃にて、５−１０分間、３５０−４００ｇ
／ｌのクロム酸および２５％硫酸を含む水溶液中で洗浄
することができる。これらの洗浄温度は例示であり、制
限的なものでない。 洗浄は所望により、洗浄液中に基
質を浸漬することにより行うが、洗浄剤を噴霧またはプ
ランがけするか、その他の方法で表面を処理する。However, in commercial applications, many nonconductive substrate materials require cleaning because the surface is not free of dust and organic matter prior to silver deposition. The surface of such substrates is preferably cleaned by any suitable technique specific to nonconductive substrates. For example, polycarbonate, polyamide, polyvinyl chloride, polyurethane, and polyester are washed with a 5% sodium hydroxide solution at 40° C. for 10 minutes. Polystyrene is 5 at 30-40℃
- Wash with 10% sodium hydroxide solution for 20 minutes. Latex and synthetic rubber are washed in a 3% sodium hypochlorite solution for 15 minutes at room temperature. Ceramics such as aluminum oxide can be cleaned in a 20% sulfuric acid solution for 20 minutes at 60° C., with simultaneous ultrasonic agitation for at least about 5 minutes. Polyimide films can be washed in acetone. The glass can be cleaned in an aqueous solution of 0.5% hydrofluoric acid and 10% sulfuric acid, which gives a slight etching to the glass. ABS polymer at 65-70°C for 5-10 minutes at 350-400g
It can be washed in an aqueous solution containing /l chromic acid and 25% sulfuric acid. These cleaning temperatures are illustrative and not limiting. Cleaning is optionally accomplished by immersing the substrate in a cleaning solution, spraying or plunging with a cleaning agent, or otherwise treating the surface.
もし洗浄が必要な場合は、洗浄後脱塩水で表面を完全に
リンスするが、表面を乾燥させる必要はない。好適に実
施するには、工程の各所で基質の表面を脱塩（脱イオン
）水で濯ぐ。化学剤が１つの工程から次の工程に移動す
ると次の工程を妨害するため、濯ぎは完全であることが
重要である。If cleaning is required, rinse the surface thoroughly with demineralized water after cleaning, but there is no need to dry the surface. In a preferred practice, the surface of the substrate is rinsed with demineralized (deionized) water at various points in the process. It is important that the rinsing be thorough, as the transfer of chemicals from one step to the next will interfere with the next step.
基質の洗浄表面を活性化し、増感が終了すると、沈着工
程の準備に入る。活性化は少なくとも０゜００１、好ま
しくは、０．０１−０．５、最も好ましくは、０．０１
−０．２ｇ／ｌのスタンナス錫イオンを含む塩希薄活性
化溶液中で行う。「スタンナス」という形容詞は塩のス
ズイオンが１２、または（ＩＩ）の酸化状態にあること
を示すものである。好ましい塩の例として、塩化第１ス
ズ（Ｓ ｎＣ１、）、フッ化第１スズ（Ｓｎｏｗ）があ
る。所定の塩を酸性化した脱塩水に溶解し、活性化溶液
を調製する。溶液のｐ）Ｉ値は、好ましくは、約１．２
約３．５、最も好ましくは、約２，５であり、塩酸の所
要Ｍを添加して調節する。活性化溶液は新たに調製する
のが好ましく、１８以」−貯蔵しないほうがよいが、溶
液の寿命はより希薄な濃度の方が長い。Once the cleaned surface of the substrate has been activated and sensitized, it is ready for the deposition step. Activation is at least 0°001, preferably 0.01-0.5, most preferably 0.01
- Carry out in a salt dilute activation solution containing 0.2 g/l stannous tin ions. The adjective "stannas" indicates that the tin ion of the salt is in the 12, or (II) oxidation state. Examples of preferred salts include stannous chloride (S nC1) and stannous fluoride (Snow). A predetermined salt is dissolved in acidified demineralized water to prepare an activation solution. The p)I value of the solution is preferably about 1.2
about 3.5, most preferably about 2.5, adjusted by adding the required M of hydrochloric acid. The activation solution is preferably freshly prepared and not stored for more than 18", but the life of the solution is longer at more dilute concentrations.
活性化溶液中での表面処理は、好ましくは、室温にて約
５−３０分間行う。処理終了後、表面の溶液を除去し、
脱塩水で完全に濯ぐが乾燥させない。Surface treatment in the activation solution is preferably carried out at room temperature for about 5-30 minutes. After the treatment is completed, remove the solution on the surface,
Rinse thoroughly with demineralized water but do not dry.
活性化し、濯いだ基質は沈着溶液に移す。移動は好まし
くは、直ぐに行うが、実験結果から、活性化基質は脱塩
水中で少なくとも数日間は貯蔵し得ることが判明してい
る。The activated and rinsed substrate is transferred to the deposition solution. Transfer is preferably carried out immediately, but experimental results have shown that the activated substrate can be stored in demineralized water for at least several days.
銀沈着溶液は好ましくは新たに調製し、長くても使用前
約４時間以内に調製し、ｐＩ］ｌａは少なくとも８以上
である。沈着溶液は、溶液を何度も使用すると沈着フィ
ルムの品質が落ちるので、好ましくは、あまり多くの基
質に使用しすぎないようにする。沈着溶液は、銀含有塩
、好ましくは、硝酸銀（ＡｇＮＯ３）を、多くとも約０
．１Ｏｇ／ｌ、好ましくは約０．０１５ｇ／ｌの効果的
な量で含む。The silver deposition solution is preferably freshly prepared, no more than about 4 hours before use, and has a pI]la of at least 8 or more. The deposition solution is preferably not used on too many substrates since repeated use of the solution will reduce the quality of the deposited film. The deposition solution contains at most about 0 silver-containing salt, preferably silver nitrate (AgNO3).
．． It is included in an effective amount of 1 Og/l, preferably about 0.015 g/l.
銀含有量が約０．ｌＯｇ／ｉ以上であると、銀元素は溶
液中で、または付着壁土に不均一に生成する。Silver content is approximately 0. When it is 1Og/i or more, the silver element is generated non-uniformly in the solution or on the attached wall soil.
好ましくは沈着溶液は２−３回使用後、捨てるので、高
価な銀が浪費される。銀含有量が効果的量より少ない場
合は、所定時間内でのフィルムを形成する銀が不足する
。Preferably, the deposition solution is used 2-3 times and then discarded, thus wasting valuable silver. If the silver content is less than the effective amount, there will be insufficient silver to form a film within a given period of time.
沈着溶液の２番目の構成要素は銀含有塩を銀元素に還元
する還元剤である。還元剤は化学的還元の完成に十分な
量が存在しなければならない。許容し得る還元剤は、ホ
ルムアルデヒド、硫酸ヒドラジン、水酸化ヒドラジンお
よび次りん酸を含む。The second component of the deposition solution is a reducing agent that reduces the silver-containing salt to elemental silver. The reducing agent must be present in an amount sufficient to complete the chemical reduction. Acceptable reducing agents include formaldehyde, hydrazine sulfate, hydrazine hydroxide and hypophosphoric acid.
還元剤は、好ましくは、約ｏ、ｏｏｔミリリットル／溶
液１？７−在する。還元剤の濃度が高ずぎると溶液中で
、または容器の壁土に銀の沈着を生じさけ、濃度か低す
ぎると、基質上の金属銀の生成に不足を生じる。The reducing agent is preferably present at about 1 to 7 milliliters of solution. Too high a concentration of the reducing agent will result in silver deposits in the solution or on the walls of the vessel; too low a concentration will result in insufficient production of metallic silver on the substrate.
沈着溶液のもう１つの要素は、沈着反応を遅延させ、還
元された金属銀を微細金属粉末として溶液から直接析出
させるのを妨げるか、または容器壁土に析出のを妨げる
のに十分な量の沈着調整剤である。採用し得る沈着調整
剤は、インバードーズとして知られている転化糖、こは
く酸、くえん酸ナトリウム、酢酸ナトリウム、水酸化ナ
トリウム、水酸化カリウム、およびアンモニアである。Another element of the deposition solution is a sufficient amount of deposit to retard the deposition reaction and prevent the reduced metallic silver from precipitating directly from the solution as a fine metal powder or onto the vessel wall soil. It is a regulator. Deposition control agents that may be employed are invert sugar, known as invardose, succinic acid, sodium citrate, sodium acetate, sodium hydroxide, potassium hydroxide, and ammonia.
沈着調整剤は、好ましくは、溶液巾約０．０５ｇ／ｌの
量で使用する。もし、少なすぎると、金属銀粒子の溶液
からの上記の析出が生じる可能性がある。多すぎると、
銀含有塩は安定しすぎて当該基質上に析出しない可能性
がある。The deposition control agent is preferably used in an amount of about 0.05 g/l solution width. If the amount is too small, the above-mentioned precipitation of metal silver particles from the solution may occur. If there are too many,
Silver-containing salts may be too stable to precipitate on the substrate.
還元剤および沈着調整剤の濃度は、基質の材質、所望の
フィルムの厚み、沈着条件および溶液中の銀の濃度によ
り変化させて、所望の結果を得る。The concentrations of the reducing agent and deposition control agent are varied depending on the substrate material, desired film thickness, deposition conditions, and concentration of silver in the solution to achieve the desired result.
例えば、薄層については、銀塩濃度は比較的低く、還元
剤および沈着調整剤の濃度も同様に低くてもよい。For example, for thin layers, the silver salt concentration may be relatively low, and the reducing agent and deposition control agent concentrations may be similarly low.
沈着溶液の調製において、溶液の各構成要素は別々に脱
塩水に溶解するのが好ましい。各予調製液を混合し、必
要ならば、先に指定した濃度になる正確な量に希釈する
。溶液を調製しながら構成要素を一緒に混合すると、不
安定かつ、早まって銀の析出を生しさせる可能性がある
。溶液を使用前に貯蔵してお場合は、不必要な沈着を防
止するために暗室に貯蔵しなければならない。In preparing the deposition solution, each component of the solution is preferably dissolved separately in demineralized water. Mix each preformulation and dilute, if necessary, to the exact amount to achieve the concentration specified above. Mixing the components together while preparing the solution can lead to instability and premature silver precipitation. If the solution is stored before use, it should be stored in the dark to prevent unnecessary deposition.
沈着銀の原料である銀塩は容易に可視領域の光線で分解
し、従って沈着工程からこのような光線を排除しなけれ
ばならない。暗所で使用する銀塩および還元剤の組み合
わせは、銀を、コロイド状で塩から還元し、基質の表面
に沈着させることを可能にする。このコロイド状態は特
に、基質表面への銀完成フィルムの良好な固着性、生体
適合性、組織相性および非毒性をもたらすのに有効であ
る。The silver salts from which the deposited silver is made are easily degraded by visible light, and such light must therefore be excluded from the deposition process. The combination of silver salt and reducing agent used in the dark allows the silver to be colloidally reduced from the salt and deposited on the surface of the substrate. This colloidal state is particularly effective in providing good adhesion of the finished silver film to the substrate surface, biocompatibility, tissue compatibility and non-toxicity.
これらの種々の性質は薄層フィルムの様々な適用に重要
である。良好な固着性はあらゆる用途に重要である。均
一な透明性は電気機器の要素として重大である。These various properties are important for various applications of thin films. Good adhesion is important in all applications. Uniform transparency is critical as a component of electrical equipment.
基質表面は適当な操作により、沈着溶液にさらされる。The substrate surface is exposed to the deposition solution by appropriate manipulation.
通常は、溶液中にちょっと浸すのが好ましいが、溶液て
噴霧またはブラシがけのような従来技術により処理し得
る。銀フィルムは銀塩の濃度により調製し得る割合で溶
液から均一に沈着する。室温にて硝酸銀の約０．０１５
ｇ／ｌの濃度で沈着率は毎秒約５オングストロームであ
るが、ある種の条件では、沈着温度が高くなれば沈着速
度ら速くなり、その率は、室温で毎秒約７オンダスト〔
ｌ−ムの速さになり得る。もし薄層が必要ならば、沈着
を制御しやすいように沈着温度は十分に低く維持する。Brief dipping in the solution is usually preferred, but treatment can be accomplished by conventional techniques such as spraying or brushing. The silver film is uniformly deposited from the solution in proportions that can be adjusted by the concentration of the silver salt. Approximately 0.015 of silver nitrate at room temperature
At a concentration of g/l the deposition rate is about 5 angstroms per second, but under certain conditions higher deposition temperatures can increase the deposition rate, which is about 7 angstroms per second at room temperature.
It can be as fast as 1-m. If thin layers are required, the deposition temperature is kept low enough to facilitate control of deposition.
すなわち、再現性のある均一な薄層て犀みが約５０オン
グストロームの場合は、１０秒間の浸漬で形成し得る。That is, a reproducibly uniform thin layer of about 50 angstroms can be formed with a 10 second immersion.
沈着時間はフィルムの厚さに比例して増大し、少なくと
も約２０００オングストロームの厚さまで増大し得ろ。Deposition time increases proportionally with film thickness and may increase up to thicknesses of at least about 2000 Angstroms.
沈着時間とフィルムの厚さの関係は指標として表され、
実際の目盛は基質と処理工程の特定の組み合わせについ
て容易に得ることができる。The relationship between deposition time and film thickness is expressed as an index,
Actual scales can be readily obtained for specific combinations of substrate and processing steps.
沈着の完了後、沈着基質を沈着溶液から取り出し、脱塩
水で洗浄するが、乾燥させない。 この時点で、基質の
処理表面に銀は金属沈着物として存在する。ある適用に
対してはこの条件を使用することができるが、使用中の
化学および物理的変化を避けるために安定化させるのが
好ましい。金属銀沈着物はその表面を安定化溶液にさら
すことにより安定化する。この溶液は少なくとも約００
０１１好ましくは約０．００１から０，１１最も好まし
くは約０．０２か（２）０５ｇ／ｌの白金族金属（例え
ばプラチナ、パラジウム、ロノウム、イリジウム、ルテ
ニウムおよびオスミウム）または金の塩、好ましくはプ
ラチナ塩を希塩酸に溶解させることにより調製される。After the deposition is complete, the deposition substrate is removed from the deposition solution and washed with demineralized water, but not dried. At this point, the silver is present as a metallic deposit on the treated surface of the substrate. Although this condition may be used for certain applications, stabilization is preferred to avoid chemical and physical changes during use. Metallic silver deposits are stabilized by exposing their surfaces to stabilizing solutions. This solution is at least about 0.00
0.11 preferably from about 0.001 to 0.11 most preferably from about 0.02 to (2)05 g/l of a platinum group metal (such as platinum, palladium, ronium, iridium, ruthenium and osmium) or a gold salt, preferably Prepared by dissolving the platinum salt in dilute hydrochloric acid.
この希釈酸は通常の濃塩酸を煮沸して水分を除去し、こ
の酸を脱塩水てＩ）１１約３．０から約４．８に希釈し
て調製するのか好ましい。この安定化溶液は調製後８時
間以内に使用ずへきて、２−３回使用すると破棄ずべき
である。この安定化溶液は室温で少なくとも約５秒間、
好ましくは１−２０分間接触させる。This diluted acid is preferably prepared by boiling conventional concentrated hydrochloric acid to remove water and diluting this acid with demineralized water to a concentration of about 3.0 to about 4.8. This stabilizing solution should not be used within 8 hours after preparation and should be discarded after 2-3 uses. The stabilizing solution is heated at room temperature for at least about 5 seconds.
Preferably the contact period is 1-20 minutes.
安定化処理後、脱塩水中で基質表面を洗浄し、乾燥させ
る。その後、使用に供するが、付着時間により決定され
る均一な厚さの付着銀コーテイング層を打する。この方
法を使用すると一度に多くの物品をコーティングするこ
とができ、物品は不規則な寸法および形状であってもよ
い。溶液が内壁に接触することができると、小さい孔の
内面でさえコーティングすることができる。ある場合に
は、濡れおよび反応を完結させるために小さい孔に種々
の溶液を通ずことが必要な場合もある。本発明の方法を
使用すると、直径０．００２ｍｍの小さい孔にも銀をコ
ーティングすることができる。After the stabilization treatment, the substrate surface is washed in demineralized water and dried. Thereafter, for use, a deposited silver coating layer of uniform thickness determined by the deposition time is deposited. Many articles can be coated at once using this method, and the articles may be of irregular size and shape. Even the inner surfaces of small pores can be coated if the solution is allowed to contact the inner walls. In some cases, it may be necessary to pass various solutions through small holes to complete wetting and reaction. Using the method of the invention, even holes as small as 0.002 mm in diameter can be coated with silver.
前処理は溶液中の不純物に敏感である。それ故、試薬品
位の化学品および脱塩（脱イオン）水を総ての工程で使
用するのが好ましい。Pretreatment is sensitive to impurities in the solution. Therefore, it is preferred to use reagent grade chemicals and demineralized (deionized) water in all steps.
次の実施例は本発明方法およびその結果を例示するもの
で、いかなる場合においてら本発明を制限するものと考
えるべきでない。The following examples are illustrative of the method of the invention and its results and should not be considered as limiting the invention in any way.
［実施例］実施例１ポリカーボネート基質の表面に均一な銀層を沈着させた
。ポリカーボネートをまず５％水酸化ナトリウムの洗浄
液に４０℃で１０分間浸漬した後、脱塩水ですすいだ。Examples Example 1 A uniform silver layer was deposited on the surface of a polycarbonate substrate. The polycarbonate was first immersed in a 5% sodium hydroxide wash solution at 40° C. for 10 minutes and then rinsed with demineralized water.
ついで、基質をｐＨ２，５の０．０５９／リツトルふつ
化第１すず溶液に２５℃で１５分間浸漬して活性化させ
、脱塩水ですすいだ。ついで、硝酸銀０．ＯＩ５ｇ／リ
ットル、アンモニアＱ、０５ｚ（！／リットル、くえん
酸ナトリウム０．０５ｙ／リットル、転化糖０．０５１
ｊ／リツトルおよびホルムアルデヒド０．００１ｘｆ２
／リツトルを含む新製した沈着液中に浸漬することによ
り表面をめっきした。沈着工程は暗室中、室温で実施し
た。−例において、基質を２分間浸漬し、約５００オン
グストロームの厚みの銀層を得た。別の例では、基質を
５分間浸漬し、約１２００オングストロームの厚みの銀
層を得た。各場合とも、沈着完了後基質を脱塩水ですす
いだ。各場合において、表面を０．０６ｇ／リットル塩
化全溶液からなる安定化液に３５℃で３０秒間漬けると
により沈着銀層を安定化させた。ついで、安定化した基
質を脱塩水ですすぎ、圧縮空気の噴流により乾燥した。The substrate was then activated by immersion in a 0.059/liter stannous fluoride solution at pH 2.5 for 15 minutes at 25°C and rinsed with demineralized water. Then, silver nitrate 0. OI 5g/liter, ammonia Q, 05z(!/liter, sodium citrate 0.05y/liter, invert sugar 0.051
j/liter and formaldehyde 0.001xf2
The surface was plated by immersion in a freshly prepared deposition solution containing /liter. The deposition process was carried out in the dark at room temperature. - In the example, the substrate was soaked for 2 minutes, resulting in a silver layer approximately 500 angstroms thick. In another example, the substrate was soaked for 5 minutes, resulting in a silver layer approximately 1200 Angstroms thick. In each case, the substrate was rinsed with demineralized water after deposition was complete. In each case, the deposited silver layer was stabilized by immersing the surface in a stabilizing solution consisting of a 0.06 g/liter total chloride solution at 35° C. for 30 seconds. The stabilized substrate was then rinsed with demineralized water and dried with a jet of compressed air.
実施例２−７各基質として、合成ゴム、ポリエステル、ポリウレタン
、ポリ塩化ビニル、ポリスチレン、およびポリアミドを
用いて、実施例１の操作をくり返した。各場合とも沈着
は成功した。Example 2-7 The operation of Example 1 was repeated using synthetic rubber, polyester, polyurethane, polyvinyl chloride, polystyrene, and polyamide as each substrate. Deposition was successful in each case.
実施例８酸化アルミニウム基質を、２５％濃度の硫酸からなる洗
浄液に６０℃で２０分間浸漬して洗浄した。２０分間中
の５分間、洗浄液を超音波撹拌した。基質を脱塩水です
すいた。ついで、０．２ｇ／リットル塩化第１すずから
なる活性化液中に室温で１５分間入れることにより基質
を活性化し、脱塩水ですすいだ。接触時間を２０秒とす
る以外は実施例Ｉと同様に沈着液に浸漬することにより
、基質を銀で被覆し、脱塩水ですすいだ。ついで、０．
０Ｉｇ／リットル塩化白金溶液からなる安定化液に１分
間浸漬することにより酸化アルミニウムを安定化し、脱
塩水ですすぎ、乾燥した。Example 8 An aluminum oxide substrate was cleaned by immersion in a cleaning solution consisting of 25% strength sulfuric acid at 60° C. for 20 minutes. The cleaning solution was ultrasonically stirred for 5 minutes out of 20 minutes. The substrate was rinsed with demineralized water. The substrate was then activated by placing it in an activation solution consisting of 0.2 g/l stannous chloride for 15 minutes at room temperature and rinsed with demineralized water. The substrate was coated with silver by immersion in the deposition solution as in Example I, except that the contact time was 20 seconds, and rinsed with demineralized water. Then, 0.
The aluminum oxide was stabilized by immersion in a stabilizing solution consisting of 0 Ig/liter platinum chloride solution for 1 minute, rinsed with demineralized water, and dried.
実施例９別の酸化アルミニウム基質を、５％水酸化ナトリウムに
６０℃で２０分間浸漬して洗浄した後、基質を、塩酸を
含むｐＨ１，５の脱塩水ですすいた。ついで、０２ｇ／
リットル塩化第１ずず中に室温で１５分間入れることに
より基質を活性化し、脱塩水ですすいた。硝酸銀０．０
１ｙ／リツトル、アンモニア０．０５ｍ１２／リツトル
およびくえん酸ナトリウム０．０８ｇ／リットルを含む
沈着液に暗所で１５℃、９０秒間基質を浸漬することに
より、銀層を沈着した。基質を脱塩水ですすいで乾燥し
た。この実施例では安定化処理を行なわなかった。得ら
れた銀層の厚みは約３５０オンダスト［１−ムである。Example 9 Another aluminum oxide substrate was cleaned by immersion in 5% sodium hydroxide at 60° C. for 20 minutes, after which the substrate was rinsed with demineralized water containing hydrochloric acid at pH 1.5. Then, 02g/
The substrate was activated by placing it in 1/2 chloride solution for 15 minutes at room temperature and rinsing with demineralized water. silver nitrate 0.0
The silver layer was deposited by immersing the substrate in a deposition solution containing 1y/liter, 0.05 ml/liter ammonia and 0.08 g/liter sodium citrate for 90 seconds at 15 DEG C. in the dark. The substrate was rinsed with demineralized water and dried. No stabilization treatment was performed in this example. The thickness of the resulting silver layer is approximately 350 Å dust [1-mm].
実施例ＩＯポリアミド基質を、アセトン中室温で洗浄し、脱塩水で
すすいだ。ついで、０．１５ｇ／リットル塩化第１すず
および１０％アセトン含有活性化液中に３０°Ｃで１０
分間入れ、脱塩水ですすいだ。Example IO A polyamide substrate was washed in acetone at room temperature and rinsed with demineralized water. 10% at 30°C in an activation solution containing 0.15g/l stannous chloride and 10% acetone.
for a minute and rinsed with demineralized water.
実施例１と同様に沈着液に５分間浸漬することにより、
銀沈着を実施し、脱塩水ですすいだ。ついで、０．００
５９／リツトル塩化白金および０００５９／リツトル塩
化全含有液に塩酸を加えてｐｌ−（４，１にした液に入
れることにより被覆表面を安定化した。安定化処理は４
０℃で１０分間行なった。By immersing in the deposition solution for 5 minutes as in Example 1,
Silver deposition was performed and rinsed with demineralized water. Then, 0.00
The coating surface was stabilized by adding hydrochloric acid to the solution containing 59/liter platinum chloride and 00059/liter chloride to make it pl-(4,1).The stabilization treatment was 4.
The test was carried out at 0°C for 10 minutes.
実施例１１ラテックス（天然ゴム）製カテーテルの内面および外面
に銀層を沈着させた。ラテックスノートを１−５％次亜
塩素酸ナトリウム含有洗浄液に室温で２分間浸漬して洗
浄し、脱塩水ですすいだ。これを、０．０５９／リツト
ル塩化第１すすからなる活性化液中に室温で１０分間置
き、脱塩水ですすいだ。硝酸銀０．０１ｇ／リットル、
くえん酸ナトリウム０．１０−０．１２９／リットルお
よびｐ ｌ−（を約８．５−約９．５にするに足る量の
アンモニアを含む浴にラテックスを入れることにより、
銀を沈着させた。銀層を、ｐＨ約４．１の塩酸中０１％
塩化白金液に室温で１分間入れて安定させた。Example 11 A silver layer was deposited on the inner and outer surfaces of a latex (natural rubber) catheter. Latex notebooks were cleaned by immersion in a cleaning solution containing 1-5% sodium hypochlorite for 2 minutes at room temperature and rinsed with demineralized water. This was placed in an activation solution consisting of 0.059/liter soot chloride for 10 minutes at room temperature and rinsed with demineralized water. Silver nitrate 0.01g/liter,
By placing the latex in a bath containing 0.10-0.129/liter of sodium citrate and sufficient ammonia to bring the p l-( to about 8.5 to about 9.5,
Deposited silver. The silver layer was dissolved in 0.1% hydrochloric acid with a pH of approximately 4.1.
It was stabilized by placing it in a platinum chloride solution for 1 minute at room temperature.
実施例Ｉ２はうけい酸カラス板を、０５％ふつ化水素酸と１０％硫
酸からなる洗浄液に室温で５分間浸漬し、脱塩水で充分
すすいだ。これを、０．ＯＩ％塩化第１すす液中で活性
化し、すすいだ。つぎに、０．０５ｙ／リツトル硝酸銀
を０．０２％ヒドラジン水和物還元剤並びにｐＨ８，５
にする水酸化ナトリウムおよびアンモニアと共に含む溶
液に１０分間漬けた。すすいだ後、０．０５９／リツト
ル塩化パラジウム酸性液中で安定化し、乾燥した。Example I2 A silicic acid glass plate was immersed in a cleaning solution consisting of 0.5% hydrofluoric acid and 10% sulfuric acid for 5 minutes at room temperature, and thoroughly rinsed with demineralized water. This is 0. Activated in OI% chloride first soot and rinsed. Next, 0.05y/liter silver nitrate was added to 0.02% hydrazine hydrate reducing agent and pH 8.5.
Soaked in a solution containing sodium hydroxide and ammonia for 10 minutes. After rinsing, it was stabilized in 0.059/liter palladium chloride acid solution and dried.
実施例１３Δｒ３ Ｓプラスデックポリマー基質を、３５０９／リ
ツトルのクロム酸および２５％硫酸含有液中、６７°Ｃ
で５分間洗浄した。ずずいた後、基質に００５ｇ／リッ
１−ル塩化第１すすを噴霧し、すすいだ。０．０１ｇ／
リットル硝酸銀、０．０５ｙ／リツトル酢酸ナトリウム
、０．０１ｉＱ／リツトル硫酸ヒドラジンおよびｐＨ９
，０にする量のアンモニアからなる溶液に基質を５分間
浸漬して銀を沈着させた。銀のフィルムを０．１％塩化
白金酸性溶液中で安定化させた。Example 13 A Δr3S Plusdec polymer substrate was incubated at 67° C. in a solution containing 3509/liter chromic acid and 25% sulfuric acid.
and washed for 5 minutes. After soaking, the substrate was sprayed with 0.005 g/liter of soot chloride and rinsed. 0.01g/
liter silver nitrate, 0.05y/liter sodium acetate, 0.01iQ/liter hydrazine sulfate and pH 9
The silver was deposited by immersing the substrate for 5 minutes in a solution consisting of . The silver film was stabilized in an acidic 0.1% platinum chloride solution.
実施例１４１バツチ２５カテーテルのラテックスカテーテルバッチ
を実施例１１の方法を用いて銀被覆し、その後抗微生物
活性を試験した。全部のカテーテルが非被覆ラテックス
カテーテルに較べて微生物活性に対する抵抗の増加を示
したが、これはバッチ法が高収率の被覆カテーテルを得
るに成功したことを意味する。Example 14 Latex catheter batches of 25 catheters per batch were silver coated using the method of Example 11 and then tested for antimicrobial activity. All catheters showed increased resistance to microbial activity compared to uncoated latex catheters, meaning that the batch process was successful in obtaining a high yield of coated catheters.
実施例１５ヒドロゲル被覆ラテックスカテーテルを、実施例１１の
方法によりさらに銀層で被覆した。Example 15 A hydrogel coated latex catheter was further coated with a silver layer by the method of Example 11.
実施例１６実施例１１を反復後、慣用浸漬法を用いて銀被覆上にヒ
ドロゲル層を被覆した。Example 16 After repeating Example 11, a hydrogel layer was coated onto the silver coating using a conventional dipping method.
実施例１７ポリウレタンカテーテルを実施例１の方法により銀被覆
した。Example 17 A polyurethane catheter was silver coated by the method of Example 1.
実施例１８テフロン（ポリテトラフルオロエチレン）被覆ラテック
スカテーテルを、まず液体ナトリウム中でテフロン被覆
をエツチングした後実施例１１の方法で銀被覆した。Example 18 A Teflon (polytetrafluoroethylene) coated latex catheter was silver coated in the manner of Example 11 after first etching the Teflon coating in liquid sodium.
実施例１９ポリエチレンびんの内側を実施例１による本発明法によ
り銀被覆してバリヤー被覆を施した。Example 19 The inside of a polyethylene bottle was coated with silver according to the method of the invention according to Example 1 to provide a barrier coating.
実施例２０実施例１９の本発明法および従来技術の電解沈着法で製
造したラテックス試料上の銀層の付着塵を、いくつかの
方法により定性的および定量的に評価した。１つの方法
では、超音波エネルギーを試料に導入し、銀層と基質間
の結合が銀層が除去できる程度に弱まるまで増加させた
。本発明法で製造した試料は、電解被覆試料に較べて、
銀層を除き得るまでに４倍多い超音波エネルギーに耐え
た。別の試料の界面を電子顕微鏡で観察した。各場合と
し界面は小孔を有していた。本発明法の試料の孔径は３
オングストロ一ム未満であり、電解法試料の孔径は＋５
−２０オングストロームであった。孔径が小さいことは
、本発明法で製造した試料の界面特性がすぐれているこ
とを示す。Example 20 Dust deposits on silver layers on latex samples produced by the inventive method of Example 19 and the prior art electrolytic deposition method were qualitatively and quantitatively evaluated by several methods. In one method, ultrasonic energy was introduced into the sample and the bond between the silver layer and the substrate was increased until the bond between the silver layer and the substrate was weakened enough that the silver layer could be removed. Compared to the electrolytically coated sample, the sample produced by the method of the present invention has
It withstood four times more ultrasonic energy before the silver layer could be removed. The interface of another sample was observed using an electron microscope. In each case the interface had small pores. The pore size of the sample according to the present invention is 3
The pore size of the electrolytic sample is +5
-20 angstroms. A small pore size indicates that the sample produced by the method of the present invention has excellent interfacial properties.
実施例２１種々の組成と被覆をもつ若干数のカテーテルを製造した
。本発明法により銀被覆カテーテルを製造した。各カテ
ーテルのｌ０ｃｍ’領域を、培地５１１ｇを含むバイア
ルに入れた。３７°Ｃで４８時間インキュヘーノヨン後
、抽出液を培地で希釈して最終抽出液濃度５．２５．５
０．７５および１００％とした。マウス繊維芽セルライ
ンＬ９２９の単層細胞を、プラスデック製マルチウェル
プレート中に樹立した。細胞培地１ｘ１２を希釈カテー
テル抽出液で置換した。プレートをさらに４８時間イン
キュベーションした。抽出物濃度はトリブリケートで製
造、試験した。Example 21 Several catheters were manufactured with various compositions and coatings. A silver-coated catheter was manufactured by the method of the present invention. A 10 cm' area of each catheter was placed in a vial containing 511 g of medium. After incubation at 37°C for 48 hours, the extract was diluted with culture medium to a final extract concentration of 5.25.5.
0.75 and 100%. Cell monolayers of mouse fibroblast cell line L929 were established in multiwell plates manufactured by Plasdec. 1 x 12 cell media were replaced with diluted catheter extract. Plates were incubated for an additional 48 hours. Extract concentrations were prepared and tested in tribricate.
培養終了後１時間曲に、各ウェルに３１−１−チミジン
１．０マイクロキユリーを添加した。細胞を水冷した１
、５％過塩素酸ですすぎ、各ウェルに５％過塩素酸０．
７ｘ（ｌを加え、ウェルを６５℃で１時間加熱した。冷
却後、液体をノンデレージョン・バイアルに移し、カウ
ント７分を記録した。One hour after the end of the culture, 1.0 microcrystalline 31-1-thymidine was added to each well. Water-cooled cells 1
, rinse with 5% perchloric acid, and add 0.0% of 5% perchloric acid to each well.
7x (l) was added and the wells were heated for 1 hour at 65°C. After cooling, the liquid was transferred to a nondestructive vial and a count of 7 minutes was recorded.
結果を、対照に対するカウント７分平均％として、抽出
物濃度軸に対してプロットした。対照の５０％まで取り
込みが低下する抽出物濃度をＥＣ−ｏと表示し、各物質
について測定した。ｒｃｓｏ値が高いほど、カテーテル
による尿道炎症が少ないことが知られている。Results were plotted against the extract concentration axis as a 7 minute average % of counts relative to the control. The extract concentration at which the uptake was reduced to 50% of the control was designated as EC-o and was determined for each substance. It is known that the higher the rcso value, the less urethral inflammation caused by the catheter.
カテーテル材料および被覆をＩＣ５ｏ値と共に示すと、
ラテックス・・・２１．７、銀被覆ラテックス・・・７
１．２、硝酸銀被覆ラテックス・・・３６．３、硫酸銀
被覆ラテックス・・・４３゜８、テフロン被覆ラテック
ス・・・５５．３、銀被覆テフロン・・・８１２、硝酸
銀被覆テフロン・・・６２．４、硫酸銀被覆テフロン・
・・６４９、ノリコーン・・・毒性なし、銀被覆シリコ
ーン・・・毒性なし、硝酸銀被覆シリコーン・・・６６
．４、硫酸銀被覆シリコーン・・・７５゜６である。銀
被覆したカテーテル材料は、非被覆材料および銀塩被覆
材料に較べてｒｃｓｏ値がすぐれている。Catheter materials and coatings with IC5o values:
Latex...21.7, Silver coated latex...7
1.2, Silver nitrate coated latex...36.3, Silver sulfate coated latex...43°8, Teflon coated latex...55.3, Silver coated Teflon...812, Silver nitrate coated Teflon...62 .4, Silver sulfate coated Teflon・
...649, Noricone...non-toxic, silver-coated silicone...non-toxic, silver nitrate-coated silicone...66
．． 4. Silver sulfate coated silicone...75°6. Silver coated catheter materials have superior rcso values compared to uncoated and silver salt coated materials.
実施例２２ソニートモナス・エルギノーザ（Ｐ 、 ａｅｒｕｇｉ
ｎｏｓａ）を含む人口尿を、ラテックス製および実施例
１１法の銀被覆ラテックス製のカテーテルに循環させた
。１０時時間型で循環後、試験のため各カテーテルから
とったディスクを細菌可視化処理後に走査電子顕微鏡中
に移した。視検の結果、当初はどの材料にも細菌細胞が
ないことがわかった。人口尿に１０分間露出後、ラテッ
クス試料は相当数の細菌を示したが、銀被覆試料には可
視細菌がなかった。１０時間露出後、ラテックスディス
クは付着細菌により完全にふさがれていたが、銀被覆ラ
テックスディスクはコロニー化が認められなかった。Example 22 Sonytomonas aeruginosa (P, aerugi
Artificial urine containing 10% of the total amount of sterilized urine was circulated through a latex catheter and a silver-coated latex catheter according to the Example 11 method. After circulation at 10 o'clock, the disks taken from each catheter for testing were transferred into a scanning electron microscope after bacterial visualization. Visual inspection initially revealed that none of the materials contained bacterial cells. After 10 minutes of exposure to artificial urine, the latex sample showed a significant number of bacteria, while the silver-coated sample had no visible bacteria. After 10 hours of exposure, the latex discs were completely occluded with adherent bacteria, whereas the silver-coated latex discs were not colonized.
この発明は、種々のタイプと形状の不導性基質を銀の薄
層で被覆する方法を提供するものである。The present invention provides a method for coating nonconductive substrates of various types and shapes with a thin layer of silver.
これらの銀層は、特に医療用、光透過用および障壁用の
用途に有利に使用され得る。アクセス装置、リード装置
、インブラント、手袋、コンドーム、カテーテルおよび
傷用医療補助品（ｗｏｕｌｄ ｄｒｅｓｓｉｎｇ）の
ような医療用装置を被覆することができる。These silver layers can be used advantageously in particular in medical, light-transmitting and barrier applications. Medical devices such as access devices, lead devices, implants, gloves, condoms, catheters and wound dressings can be coated.
びんを被覆してガスバリヤ−を設けることができる。透
明不導基質を銀の薄い不可視フィルムで被覆して熱エネ
ルギーを吸収させることができる。The bottle can be coated to provide a gas barrier. A transparent non-conductive substrate can be coated with a thin invisible film of silver to absorb thermal energy.
本発明の銀フィルムは、可視化に要するより少ない厚み
で適用するのに最もすぐれている。The silver film of the present invention is best applied at less thickness than required for visualization.
このように、本発明の方法は不導基質上に均一な銀の薄
層を製造する技術に大きな改善をもたらずものである。Thus, the method of the present invention does not represent a significant improvement in the art of producing uniform thin layers of silver on nonconducting substrates.
このフィルムは、薄い、温和な湿式の（ｓｅｔ）化学剤
溶液を用いて商業装置で再現的に製造することができる
。説明を目的として本発明の特定の実施態様を詳細に記
載したが、本発明の精神と範囲を逸脱することなく種々
の修飾が可能である。したがって、本発明は特許請求の
範囲による以外の制限は受けるものではない。This film can be reproducibly produced in commercial equipment using thin, mild set chemical solutions. Although specific embodiments of the invention have been described in detail for purposes of illustration, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the scope of the claims.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34701689A | 1989-05-04 | 1989-05-04 | |
| US347,016 | 1989-05-04 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7320886ADivisionJP3030687B2 (en) | 1989-05-04 | 1995-12-08 | Silver layer deposition on non-conductive substrates |
| JP7320892ADivisionJPH08333687A (en) | 1989-05-04 | 1995-12-08 | Deposition of silver layer on nonconductive substrate |
| Publication Number | Publication Date |
|---|---|
| JPH03219085Atrue JPH03219085A (en) | 1991-09-26 |
| JP2645431B2 JP2645431B2 (en) | 1997-08-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2118482AExpired - LifetimeJP2645431B2 (en) | 1989-05-04 | 1990-05-07 | Method for producing alkali titanate fiber |
| JP7320892AWithdrawnJPH08333687A (en) | 1989-05-04 | 1995-12-08 | Deposition of silver layer on nonconductive substrate |
| JP7320886AExpired - LifetimeJP3030687B2 (en) | 1989-05-04 | 1995-12-08 | Silver layer deposition on non-conductive substrates |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7320892AWithdrawnJPH08333687A (en) | 1989-05-04 | 1995-12-08 | Deposition of silver layer on nonconductive substrate |
| JP7320886AExpired - LifetimeJP3030687B2 (en) | 1989-05-04 | 1995-12-08 | Silver layer deposition on non-conductive substrates |
| Country | Link |
|---|---|
| US (4) | US5395651A (en) |
| EP (3) | EP0693576A1 (en) |
| JP (3) | JP2645431B2 (en) |
| AT (1) | ATE134719T1 (en) |
| AU (1) | AU642872B2 (en) |
| CA (1) | CA2016081C (en) |
| DE (1) | DE69025495T2 (en) |
| DK (1) | DK0400349T3 (en) |
| ES (1) | ES2086328T3 (en) |
| FI (1) | FI95816C (en) |
| GR (1) | GR3019899T3 (en) |
| NO (1) | NO304746B1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246661A (en)* | 2001-02-20 | 2002-08-30 | Toshiba Corp | Thermoelectric processing system |
| JP2013544972A (en)* | 2010-11-26 | 2013-12-19 | シー・アール・バード・インコーポレーテッド | Deposition of silver layer on non-conductive substrate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI95816C (en) | 1989-05-04 | 1996-03-25 | Ad Tech Holdings Ltd | Antimicrobial article and method of making the same |
| DE4324994C1 (en)* | 1993-07-26 | 1995-02-23 | Demetron Gmbh | Equipment and sanitary articles for hospitals |
| JP3109101B2 (en)* | 1994-10-05 | 2000-11-13 | 東陶機器株式会社 | Antimicrobial solid, method for producing the same, and method for using the same |
| US5925567A (en)* | 1995-05-19 | 1999-07-20 | T. Breeders, Inc. | Selective expansion of target cell populations |
| US7214847B1 (en) | 1997-09-22 | 2007-05-08 | Argentum Medical, L.L.C. | Multilayer conductive appliance having wound healing and analgesic properties |
| US8801681B2 (en)* | 1995-09-05 | 2014-08-12 | Argentum Medical, Llc | Medical device |
| US8455710B2 (en) | 1997-09-22 | 2013-06-04 | Argentum Medical, Llc | Conductive wound dressings and methods of use |
| US5814094A (en)* | 1996-03-28 | 1998-09-29 | Becker; Robert O. | Iontopheretic system for stimulation of tissue healing and regeneration |
| US6087549A (en)* | 1997-09-22 | 2000-07-11 | Argentum International | Multilayer laminate wound dressing |
| US6861570B1 (en)* | 1997-09-22 | 2005-03-01 | A. Bart Flick | Multilayer conductive appliance having wound healing and analgesic properties |
| US5709672A (en)* | 1995-11-01 | 1998-01-20 | Texas Tech University Health Sciences Center | Silastic and polymer-based catheters with improved antimicrobial/antifungal properties |
| US5871816A (en)* | 1996-08-09 | 1999-02-16 | Mtc Ltd. | Metallized textile |
| CH692135A5 (en)* | 1997-08-20 | 2002-02-28 | Tradition Establishment | A process for the metalizing coating of artifacts. |
| US6605751B1 (en) | 1997-11-14 | 2003-08-12 | Acrymed | Silver-containing compositions, devices and methods for making |
| US6120639A (en)* | 1997-11-17 | 2000-09-19 | Macdermid, Incorporated | Method for the manufacture of printed circuit boards |
| US6596401B1 (en) | 1998-11-10 | 2003-07-22 | C. R. Bard Inc. | Silane copolymer compositions containing active agents |
| US6475644B1 (en) | 1998-11-18 | 2002-11-05 | Radiovascular Systems, L.L.C. | Radioactive coating solutions methods, and substrates |
| WO2000051659A1 (en)* | 1999-03-05 | 2000-09-08 | Matson Louis R | Surface-modified bioactive surgical implants suppressing tissue growth |
| US6716895B1 (en) | 1999-12-15 | 2004-04-06 | C.R. Bard, Inc. | Polymer compositions containing colloids of silver salts |
| US7179849B2 (en) | 1999-12-15 | 2007-02-20 | C. R. Bard, Inc. | Antimicrobial compositions containing colloids of oligodynamic metals |
| US6579539B2 (en) | 1999-12-22 | 2003-06-17 | C. R. Bard, Inc. | Dual mode antimicrobial compositions |
| AU2742401A (en) | 1999-12-30 | 2001-07-16 | Acrymed | Methods and compositions for improved delivery devices |
| US6387542B1 (en)* | 2000-07-06 | 2002-05-14 | Honeywell International Inc. | Electroless silver plating |
| US6361824B1 (en) | 2000-07-31 | 2002-03-26 | Nanocrystal Imaging Corp. | Process for providing a highly reflective coating to the interior walls of microchannels |
| DE10054544A1 (en)* | 2000-11-01 | 2002-05-08 | Atotech Deutschland Gmbh | Process for the chemical metallization of surfaces |
| US6645557B2 (en)* | 2001-10-17 | 2003-11-11 | Atotech Deutschland Gmbh | Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions |
| US7129404B2 (en)* | 2001-11-08 | 2006-10-31 | Yamaha Corporation | Keyboard musical instrument having keys regulated with stable key balance pieces and process for fabricating keys |
| JP2005511144A (en) | 2001-12-03 | 2005-04-28 | シー・アール・バード・インク | Microbial-resistant medical device, microbial-resistant polymer coating and production method thereof |
| US6638993B2 (en)* | 2001-12-12 | 2003-10-28 | Milliken & Company | Colored antimicrobial vulcanized rubber articles |
| US7008979B2 (en)* | 2002-04-30 | 2006-03-07 | Hydromer, Inc. | Coating composition for multiple hydrophilic applications |
| US8486426B2 (en) | 2002-07-29 | 2013-07-16 | Kimberly-Clark Worldwide, Inc. | Methods and compositions for treatment of dermal conditions |
| US6979478B1 (en) | 2002-08-01 | 2005-12-27 | Hilemn, Llc | Paint for silver film protection and method |
| EP1536848B1 (en)* | 2002-09-10 | 2007-11-14 | Prof. Dr. Josef-Peter Guggenbichler,Dr. Christoph Cichos GBR Antimicrobial Argentum Technologies | Methods for producing an anti-microbial plastic product |
| US7628784B2 (en)* | 2003-01-06 | 2009-12-08 | C. R. Bard, Inc. | Balloon catheter with improved resistance to non-deflation |
| US7482034B2 (en)* | 2003-04-24 | 2009-01-27 | Boston Scientific Scimed, Inc. | Expandable mask stent coating method |
| CA2678624C (en)* | 2003-05-16 | 2012-11-06 | Exciton Technologies Inc. | Deposition products, composite materials and processes for the production thereof |
| DE10328261B4 (en)* | 2003-06-23 | 2007-10-25 | Beiersdorf Ag | Disinfecting coating with silver coating and its use |
| NZ543643A (en)* | 2003-06-23 | 2007-09-28 | Beiersdorf Ag | Antimicrobial wound dressing with two layers and antimicrobial metal between layers but not on exterior |
| US8425926B2 (en) | 2003-07-16 | 2013-04-23 | Yongxing Qiu | Antimicrobial medical devices |
| US8636721B2 (en)* | 2003-11-20 | 2014-01-28 | Henry M. Jackson Foundation For The Advancement Of Military Medicine, Inc. | Portable hand pump for evacuation of fluids |
| US20050123621A1 (en)* | 2003-12-05 | 2005-06-09 | 3M Innovative Properties Company | Silver coatings and methods of manufacture |
| JP4320447B2 (en)* | 2004-02-03 | 2009-08-26 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder and method for producing the same |
| US8361553B2 (en)* | 2004-07-30 | 2013-01-29 | Kimberly-Clark Worldwide, Inc. | Methods and compositions for metal nanoparticle treated surfaces |
| WO2006015317A2 (en) | 2004-07-30 | 2006-02-09 | Acrymed, Inc. | Antimicrobial devices and compositions |
| AU2005280443B2 (en) | 2004-07-30 | 2011-02-03 | Avent, Inc. | Antimicrobial silver compositions |
| US20060034899A1 (en)* | 2004-08-12 | 2006-02-16 | Ylitalo Caroline M | Biologically-active adhesive articles and methods of manufacture |
| US20060035039A1 (en)* | 2004-08-12 | 2006-02-16 | 3M Innovative Properties Company | Silver-releasing articles and methods of manufacture |
| JP4805270B2 (en)* | 2004-08-23 | 2011-11-02 | ノーブル ファイバー テクノロジーズ エルエルシー | Metal processing method for polymer foam for production of antimicrobial material and filtration material |
| WO2006034249A2 (en) | 2004-09-20 | 2006-03-30 | Acrymed, Inc. | Antimicrobial amorphous compositions |
| US8337475B2 (en) | 2004-10-12 | 2012-12-25 | C. R. Bard, Inc. | Corporeal drainage system |
| US8399027B2 (en)* | 2005-04-14 | 2013-03-19 | 3M Innovative Properties Company | Silver coatings and methods of manufacture |
| DK1901723T3 (en)* | 2005-06-27 | 2011-06-06 | Smith & Nephew | Antimicrobial materials |
| JP2008546832A (en)* | 2005-06-27 | 2008-12-25 | スミス アンド ネフュー ピーエルシー | Antibacterial biguanide metal complex |
| KR100733788B1 (en) | 2005-08-16 | 2007-07-02 | 이기학 | Silver film formation method |
| US8177772B2 (en) | 2005-09-26 | 2012-05-15 | C. R. Bard, Inc. | Catheter connection systems |
| US20070166399A1 (en)* | 2006-01-13 | 2007-07-19 | 3M Innovative Properties Company | Silver-containing antimicrobial articles and methods of manufacture |
| GB0601687D0 (en)* | 2006-01-27 | 2006-03-08 | Smith & Nephew | Antimicrobial materials |
| DE102006004628A1 (en)* | 2006-01-31 | 2007-08-09 | Landau, Uwe, Prof. Dr. | Oligodynamically effective device and process for its preparation |
| MX321310B (en)* | 2006-02-08 | 2014-06-24 | Kimberly Clark Co | METHODS AND COMPOSITIONS FOR SURFACES TREATED WITH METAL NANOPARTICLES. |
| JP2007217239A (en)* | 2006-02-17 | 2007-08-30 | Taiko Pharmaceutical Co Ltd | Chlorine dioxide generating composition |
| US20070218096A1 (en)* | 2006-03-14 | 2007-09-20 | Debbie Wooley | Medical equipment and methods of making and using the same |
| ES2379989T3 (en) | 2006-04-07 | 2012-05-07 | Bactiguard Ab | Novel antimicrobial substrates and their uses |
| EP2015722B1 (en) | 2006-04-28 | 2016-11-16 | Avent, Inc. | Antimicrobial site dressings |
| US7661430B2 (en)* | 2006-05-19 | 2010-02-16 | Richard Mason | Antimicrobial dental appliances including mouthguards and mouthpieces |
| EP2026846A4 (en)* | 2006-06-05 | 2010-09-29 | Bactiguard Ab | A polymer matrix, uses thereof and a method of manufacturing the same |
| DE102006029947B4 (en)* | 2006-06-29 | 2013-01-17 | Basf Se | Method for applying a metallic cover layer to a high-temperature superconductor |
| DE102006038940A1 (en)* | 2006-08-18 | 2008-02-21 | Bayer Materialscience Ag | Dispersions of nanoureas containing active ingredients |
| WO2008036787A1 (en)* | 2006-09-22 | 2008-03-27 | C.R. Bard, Inc. | Antimicrobial compositions containing gallium |
| RU2315649C1 (en)* | 2006-10-12 | 2008-01-27 | Александр Сергеевич Парфенов | Composite filtering material and the method of its preparation |
| US20100098949A1 (en)* | 2006-10-18 | 2010-04-22 | Burton Scott A | Antimicrobial articles and method of manufacture |
| GB2445729A (en)* | 2007-01-22 | 2008-07-23 | Marnich Hygiene Ltd | A water based anti-bacterial / microbial lacquer for non porous surfaces |
| CA2675505C (en)* | 2007-01-31 | 2015-01-06 | Novartis Ag | Antimicrobial medical devices including silver nanoparticles |
| AU2008326154B2 (en)* | 2007-10-30 | 2013-12-12 | Uti Limited Partnership | Method and system for sustained-release of sclerosing agent |
| RU2357784C2 (en)* | 2007-12-17 | 2009-06-10 | Александра Анатольевна Ревина | Material with polyfunctional activity based on open-porous polyethylene containing nanoparticles of silver, and method for its production |
| RU2355471C1 (en)* | 2008-03-19 | 2009-05-20 | Государственное образовательное учреждение высшего профессионального образования "Воронежский государственный университет" | Method of nanocomposite preparation |
| FR2930121B1 (en)* | 2008-04-18 | 2010-05-21 | Shiseido Int France | PERFUME BOTTLE |
| CN102076731B (en)* | 2008-05-29 | 2013-11-27 | 巴斯夫欧洲公司 | Antimicrobial composition containing antimicrobials covalently linked with polyurethane-silica interpenetrating network |
| RU2375510C1 (en)* | 2008-06-10 | 2009-12-10 | Зао "Цнтб" | Method for biocide treatment of tanning semi-finished product |
| EP2177238B1 (en) | 2008-10-14 | 2016-11-09 | Dentsply IH AB | Medical device with controllably releasable antibacterial agent |
| CN101736329B (en)* | 2008-11-21 | 2012-02-22 | 比亚迪股份有限公司 | A kind of polyimide membrane activation liquid and the method for polyimide membrane metallization |
| FR2938850B1 (en)* | 2008-11-27 | 2011-04-29 | Sgd Sa | METHOD FOR MANUFACTURING A HOLLOW BODY HAVING A METALLIC GLASS INTERIOR SURFACE AND HOLLOW CORRESPONDING BODY |
| RU2412292C2 (en)* | 2009-01-12 | 2011-02-20 | Тахир Хусанович Холматов | Method to treat fabric |
| GB0903642D0 (en) | 2009-02-27 | 2009-09-30 | Bae Systems Plc | Electroless metal deposition for micron scale structures |
| RU2400286C1 (en)* | 2009-03-13 | 2010-09-27 | Валерий Павлович Герасименя | Filter material for cleaning liquid and gaseous substances and method of obtaining said material |
| US8318260B2 (en)* | 2009-05-15 | 2012-11-27 | Nano CMS Co., Ltd | Method for electroless deposition of nano metallic silver and reflector of high reflectance deposited by nano metallic silver using the same |
| DK2338535T3 (en) | 2009-12-18 | 2012-09-24 | Dentsply Ih Ab | Medical device for short-term use with fast-releasing antibacterial agent |
| FR2958944B1 (en) | 2010-04-19 | 2014-11-28 | Pegastech | METHOD FOR COATING A SURFACE OF A SUBSTRATE OF NON-METALLIC MATERIAL WITH A METAL LAYER |
| DE102010035867A1 (en) | 2010-08-30 | 2012-03-01 | Retec Kunststofftechnik Gmbh | Prosthesis starting material, in particular for dental prostheses |
| JP5840454B2 (en)* | 2011-10-27 | 2016-01-06 | 上村工業株式会社 | Reduced electroless silver plating solution and reduced electroless silver plating method |
| DE102012023349B4 (en) | 2012-11-29 | 2022-10-13 | Hochschule München | Process and device for the structured coating of the inside of a hose or pipe |
| US10316161B2 (en) | 2017-03-16 | 2019-06-11 | International Business Machines Corporation | Method of making highly porous polyhexahydrotriazines containing antimicrobial agents |
| SE545102C2 (en) | 2018-04-25 | 2023-04-04 | Bactiguard Ab | A surface coating for use in the prophylaxis of allergy |
| SE2250455A1 (en) | 2022-04-12 | 2023-10-13 | Bactiguard Ab | Silver free surface coating |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329943A (en)* | 1976-08-27 | 1978-03-20 | Okubo Kiyomitsu | Aromatic compound |
| JPS59218157A (en)* | 1983-05-20 | 1984-12-08 | バックスター インターナショナル インコーポレーテッド | Production of anti-bacterial catheter |
| JPS63145660A (en)* | 1986-09-05 | 1988-06-17 | アメリカン・サイアナミド・カンパニー | Coating of surgical filament |
| JPS6468478A (en)* | 1987-09-07 | 1989-03-14 | Agency Ind Science Techn | Metal plating method using silver hydrosol |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3184376A (en)* | 1965-05-18 | Method of producing antisepticcomposition | ||
| US1281262A (en)* | 1915-09-21 | 1918-10-15 | Felix O Andres | Process of coating with precious metal. |
| US1642089A (en)* | 1920-01-08 | 1927-09-13 | Gen Zeolite Company | Process and material for sterilization of liquids |
| US1685204A (en)* | 1920-10-08 | 1928-09-25 | Gen Zeolite Company | Liquid-treating material and method of making same |
| US1557234A (en)* | 1923-09-14 | 1925-10-13 | Bechhold Heinrich | Filter |
| US1557235A (en)* | 1924-07-01 | 1925-10-13 | Becthold Heinrich | Filter |
| US1691755A (en)* | 1927-07-05 | 1928-11-13 | Henry F Buttner | Dental plate and process for plating same |
| US2283883A (en)* | 1938-07-27 | 1942-05-19 | Sacora Soc An Commercio Olii R | Method of preparing oligodynamic filters |
| US2363354A (en)* | 1939-11-16 | 1944-11-21 | Libbey Owens Ford Glass Co | Method of making mirrors |
| US2317876A (en)* | 1941-03-31 | 1943-04-27 | Pittsburgh Plate Glass Co | Manufacture of mirrors |
| US2459896A (en)* | 1945-01-18 | 1949-01-25 | Schwarz George | Silver impregnation |
| US2459897A (en)* | 1945-07-25 | 1949-01-25 | Schwarz George | Silver impregnation |
| US2421079A (en)* | 1946-01-31 | 1947-05-27 | Narcus Harold | Method for silvering nonconductive materials |
| GB646921A (en)* | 1947-04-24 | 1950-11-29 | Standard Telephones Cables Ltd | Metallisation of non-metallic surfaces |
| US2602757A (en)* | 1948-04-09 | 1952-07-08 | Morris S Kantrowitz | Method and composition for producing silver coatings |
| US2653893A (en)* | 1948-08-20 | 1953-09-29 | Isabella B Romans | Methods of applying oligodynamic silver and articles produced thereby |
| US2689191A (en)* | 1948-12-10 | 1954-09-14 | Rca Corp | Formation of reflecting coatings |
| FR1009633A (en)* | 1950-02-02 | 1952-06-03 | Pour Le Perfectionnement Des A | Silver metallization process |
| US2689199A (en)* | 1950-06-27 | 1954-09-14 | Mario R Pesce | Nonwoven fabrics |
| US2702253A (en)* | 1950-11-01 | 1955-02-15 | Gasaccumulator Svenska Ab | Surface metallizing method |
| US2836515A (en)* | 1953-04-30 | 1958-05-27 | Westinghouse Electric Corp | Gold immersion solution for treating silver and method of applying same |
| US2879175A (en)* | 1953-10-23 | 1959-03-24 | Ericsson Telefon Ab L M | Method for producing a silver coating on a non metallic material |
| US2822289A (en)* | 1954-08-18 | 1958-02-04 | Olin Mathieson | Method of coating a surface with silver from solution |
| US2813059A (en)* | 1954-11-12 | 1957-11-12 | A O Edwards | Oligodynamic silver treating process and microbicidal product |
| US2924535A (en)* | 1954-12-06 | 1960-02-09 | Gen Electric | Method of depositing a silver film |
| US2813056A (en)* | 1955-03-29 | 1957-11-12 | A O Edwards | Oligodynamic silver solution and process of rendering a surface microbicidal |
| US3092552A (en)* | 1958-05-19 | 1963-06-04 | Albert C Nolte | Oligodynamic silver compositions and uses |
| US2947282A (en)* | 1958-08-06 | 1960-08-02 | Brown Co D S | Microbicidal elastomer articles |
| US3214292A (en)* | 1962-09-12 | 1965-10-26 | Western Electric Co | Gold plating |
| FR1399011A (en)* | 1963-05-13 | 1965-05-14 | Device for silvering electrically non-conductive objects | |
| US3515571A (en)* | 1963-07-02 | 1970-06-02 | Lockheed Aircraft Corp | Deposition of gold films |
| US3396727A (en)* | 1964-01-06 | 1968-08-13 | Nolte Albert C Jr | Drainage tube for body fluids provided with filtering means coated with bacterial preventive material |
| US3561995A (en)* | 1967-04-03 | 1971-02-09 | M & T Chemicals Inc | Method of activating a polymer surface and resultant article |
| SE328974B (en) | 1968-04-05 | 1970-09-28 | A Bergstroem | |
| US3598126A (en)* | 1968-04-30 | 1971-08-10 | Baxter Laboratories Inc | Vascular canula for medical applications |
| US3598127A (en)* | 1968-06-06 | 1971-08-10 | James G Wepsic | Catheter having antibacterial substance therein provided with means permitting slow release of said substance |
| GB1236250A (en) | 1968-10-18 | 1971-06-23 | Welwyn Electric Ltd | Improvements in or relating to the electrodes deposition of films on substrates |
| US3657003A (en)* | 1970-02-02 | 1972-04-18 | Western Electric Co | Method of rendering a non-wettable surface wettable |
| US3695921A (en)* | 1970-09-09 | 1972-10-03 | Nat Patent Dev Corp | Method of coating a catheter |
| US3877965A (en)* | 1970-09-28 | 1975-04-15 | Rohm & Haas | Conductive nylon substrates and method of producing them |
| US3699956A (en)* | 1970-10-01 | 1972-10-24 | Tecna Corp | Percutaneous lead device |
| US3880580A (en)* | 1971-01-11 | 1975-04-29 | Polymer Research Corp Of Ameri | Method of activating polymeric materials |
| US3914520A (en)* | 1971-04-05 | 1975-10-21 | Bunker Ramo | Method for plating of plastic |
| US3798050A (en)* | 1971-05-28 | 1974-03-19 | Ppg Industries Inc | Catalytic sensitization of substrates for metallization |
| US3904792A (en)* | 1972-02-09 | 1975-09-09 | Shipley Co | Catalyst solution for electroless metal deposition on a substrate |
| US3874882A (en)* | 1972-02-09 | 1975-04-01 | Shipley Co | Catalyst solution for electroless deposition of metal on substrate |
| US3841881A (en)* | 1972-09-13 | 1974-10-15 | Rca Corp | Method for electroless deposition of metal using improved colloidal catalyzing solution |
| US4128671A (en)* | 1973-03-14 | 1978-12-05 | Reliance Electric Company | Instant silvering solution |
| FR2239539B1 (en)* | 1973-08-01 | 1976-04-30 | Rhone Poulenc Textile | |
| US4148945A (en)* | 1974-02-04 | 1979-04-10 | The Dow Chemical Company | Process of metal plating on plastics |
| US3932694A (en)* | 1974-04-04 | 1976-01-13 | Tatsuta Densen Kabushiki Kaisha | Pre-treatment method for electroless plating for producing a metal film as resistor |
| JPS576177B2 (en)* | 1974-08-22 | 1982-02-03 | ||
| US4237229A (en)* | 1975-06-10 | 1980-12-02 | W. R. Grace & Co. | Immobilization of biological material with polyurethane polymers |
| IT1041350B (en)* | 1975-07-25 | 1980-01-10 | Alfachimici Spa | SILVER-BASED ACTIVATING SOLUTION FOR ANELECTRIC COPPERING PROCESSES |
| US4027393A (en)* | 1975-09-19 | 1977-06-07 | Sybron Corporation | Method of in vivo sterilization of surgical implantables |
| US4564361A (en)* | 1975-11-18 | 1986-01-14 | Hiroshi Akiyama | Catheter |
| US4054139A (en) | 1975-11-20 | 1977-10-18 | Crossley Kent B | Oligodynamic catheter |
| US4054135A (en)* | 1976-07-23 | 1977-10-18 | Berman Robert A | Intubating pharyngeal airway |
| US4181759A (en)* | 1976-08-05 | 1980-01-01 | Nathan Feldstein | Process for metal deposition of a non-conductor substrate |
| DE2639342C3 (en)* | 1976-09-01 | 1981-01-08 | Basf Ag, 6700 Ludwigshafen | Process for the production of silver catalysts applied to supports |
| US4091128A (en)* | 1976-10-08 | 1978-05-23 | Ppg Industries, Inc. | Electroless gold plating bath |
| US4228201A (en)* | 1977-06-06 | 1980-10-14 | Nathan Feldstein | Method for rendering a non-platable semiconductor substrate platable |
| US4355083A (en)* | 1977-06-06 | 1982-10-19 | Nathan Feldstein | Electrolessly metallized silver coated article |
| US4181760A (en)* | 1977-06-06 | 1980-01-01 | Surface Technology, Inc. | Method for rendering non-platable surfaces platable |
| US4419390A (en)* | 1977-06-06 | 1983-12-06 | Nathan Feldstein | Method for rendering non-platable semiconductor substrates platable |
| US4171393A (en)* | 1977-06-20 | 1979-10-16 | Eastman Kodak Company | Electroless plating method requiring no reducing agent in the plating bath |
| US4144361A (en)* | 1977-07-06 | 1979-03-13 | Nathan Feldstein | Methods for applying metallic silver coatings |
| US4180602A (en)* | 1978-03-31 | 1979-12-25 | Bell Telephone Laboratories, Incorporated | Electroless plating of polyvinylidene fluoride |
| US4348429A (en)* | 1978-09-05 | 1982-09-07 | The Dow Chemical Company | Process for silver coating of permeable substrates |
| NL184695C (en)* | 1978-12-04 | 1989-10-02 | Philips Nv | BATH FOR THE STREAMLESS DEPOSIT OF TIN ON SUBSTRATES. |
| JPS56269A (en) | 1979-06-13 | 1981-01-06 | Mitsubishi Electric Corp | Plural layer non-electrolytic plating |
| US4350541A (en)* | 1979-08-13 | 1982-09-21 | Nippon Telegraph & Telephone Public Corp. | Doping from a photoresist layer |
| DE3065169D1 (en)* | 1979-08-31 | 1983-11-10 | Teijin Ltd | Heat wave-reflective or electrically conductive laminated structure |
| US4253463A (en)* | 1979-10-19 | 1981-03-03 | Kim Il B | Method of reducing infection utilizing an intravascular device having antiseptic metal portion |
| EP0048246B1 (en)* | 1980-03-27 | 1986-05-28 | National Research Development Corporation | Antimicrobial surgical implants |
| US4483688A (en)* | 1980-09-22 | 1984-11-20 | Hiroshi Akiyama | Catheter |
| US4404197A (en) | 1981-05-15 | 1983-09-13 | Fox Jr Charles L | Antimicrobial compositions containing 1-ethyl-6-fluoro-1,4-dihydro-4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid or metal salts thereof and silver sulfadiazine |
| US4539234A (en)* | 1981-05-27 | 1985-09-03 | Unitika Ltd. | Urethral catheter capable of preventing urinary tract infection and process for producing the same |
| US4374876A (en)* | 1981-06-02 | 1983-02-22 | Occidental Chemical Corporation | Process for the immersion deposition of gold |
| US4407865A (en)* | 1981-06-09 | 1983-10-04 | Atlantic Richfield Company | Process for coating a sterilizing filter material with silver and product formed thereby |
| US4411648A (en)* | 1981-06-11 | 1983-10-25 | Board Of Regents, The University Of Texas System | Iontophoretic catheter device |
| NL8202842A (en)* | 1982-07-14 | 1984-02-01 | Philips Nv | METHOD OF APPLYING A METAL MIRROR ON A SURFACE MADE OF AN ACRYLIC PLASTIC OR A METHACRYLATE PLASTIC. |
| US4734296A (en)* | 1982-09-27 | 1988-03-29 | Etd Technology, Inc. | Electroless plating of through-holes using pressure differential |
| US4603152A (en) | 1982-11-05 | 1986-07-29 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
| US4438688A (en) | 1983-03-07 | 1984-03-27 | Johnson Paul E | Nutcracker |
| DE3337856A1 (en)* | 1983-10-18 | 1985-04-25 | Bayer Ag, 5090 Leverkusen | METHOD FOR ACTIVATING SUBSTRATES FOR CURRENT METALIZATION |
| US4542169A (en)* | 1983-12-12 | 1985-09-17 | Rohm And Haas Company | Biomedical devices containing isothiazolones to control bacteria growth |
| US4569673A (en)* | 1984-01-12 | 1986-02-11 | Battelle Development Corporation | Bacterial barrier for indwelling catheters and other medical devices |
| JPS60232085A (en)* | 1984-04-28 | 1985-11-18 | Kanegafuchi Chem Ind Co Ltd | Method for germ-free filtration |
| US4563485A (en)* | 1984-04-30 | 1986-01-07 | The Trustees Of Columbia University In The City Of New York | Injection-resistant materials and method of making same through use of nalidixic acid derivatives |
| US4581028A (en) | 1984-04-30 | 1986-04-08 | The Trustees Of Columbia University In The City Of New York | Infection-resistant materials and method of making same through use of sulfonamides |
| US4725314A (en)* | 1984-05-07 | 1988-02-16 | Shipley Company Inc. | Catalytic metal of reduced particle size |
| US4668532A (en)* | 1984-09-04 | 1987-05-26 | Kollmorgen Technologies Corporation | System for selective metallization of electronic interconnection boards |
| US4677143A (en)* | 1984-10-01 | 1987-06-30 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
| ATE88324T1 (en)* | 1984-12-28 | 1993-05-15 | Johnson Matthey Plc | ANTIMICROBIAL COMPOSITIONS. |
| US4612337A (en)* | 1985-05-30 | 1986-09-16 | The Trustees Of Columbia University In The City Of New York | Method for preparing infection-resistant materials |
| US4886505A (en)* | 1985-06-07 | 1989-12-12 | Becton, Dickinson And Company | Antimicrobial surfaces and inhibition of microorganism growth thereby |
| US4847049A (en)* | 1985-12-18 | 1989-07-11 | Vitaphore Corporation | Method of forming chelated collagen having bactericidal properties |
| GB8616294D0 (en)* | 1986-07-03 | 1986-08-13 | Johnson Matthey Plc | Antimicrobial compositions |
| US4784647A (en)* | 1986-07-30 | 1988-11-15 | The Kendal Company | Catheter meatal pad device |
| US4737188A (en)* | 1987-05-18 | 1988-04-12 | London Laboratories Limited | Reducing agent and method for the electroless deposition of silver |
| JPS6415056A (en)* | 1987-07-09 | 1989-01-19 | Hanarou Maeda | Body indwelling tube |
| JPS6415986A (en) | 1987-07-09 | 1989-01-19 | Nec Corp | Equipment for measuring semiconductor photosensor |
| DE3725728A1 (en)* | 1987-08-04 | 1989-02-16 | Freudenberg Carl Fa | MEDICAL DEVICE AND METHOD FOR THE PRODUCTION THEREOF |
| GB8720502D0 (en)* | 1987-08-29 | 1987-10-07 | Giltech Ltd | Antimicrobial composition |
| US4915694A (en)* | 1987-10-02 | 1990-04-10 | Vitaphore Corporation | Antimicrobial wound dressing and skin fixator for percutaneous conduits |
| US4902503A (en)* | 1987-11-25 | 1990-02-20 | Unitika Ltd. | Antimicrobial latex composition |
| US5019096A (en)* | 1988-02-11 | 1991-05-28 | Trustees Of Columbia University In The City Of New York | Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same |
| US4933178A (en)* | 1988-10-07 | 1990-06-12 | Biointerface Technologies, Inc. | Metal-based antimicrobial coating |
| IE64997B1 (en)* | 1989-01-18 | 1995-10-04 | Becton Dickinson Co | Anti-infection and antithrombogenic medical articles and method for their preparation |
| FI95816C (en)* | 1989-05-04 | 1996-03-25 | Ad Tech Holdings Ltd | Antimicrobial article and method of making the same |
| DE3916648C1 (en)* | 1989-05-22 | 1990-09-06 | Fa. Carl Freudenberg, 6940 Weinheim, De | |
| US5295979A (en)* | 1992-03-27 | 1994-03-22 | P & D Medical Coatings, Inc. | Urinary catheter and system |
| US5322520A (en)* | 1992-11-12 | 1994-06-21 | Implemed, Inc. | Iontophoretic structure for medical devices |
| JPH07107441A (en)* | 1993-09-30 | 1995-04-21 | Toshiba Corp | Video signal transmitter / receiver |
| US20210334519A1 (en) | 2018-08-31 | 2021-10-28 | Nec Corporation | Information processing apparatus, method, and non-transitory storage medium |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329943A (en)* | 1976-08-27 | 1978-03-20 | Okubo Kiyomitsu | Aromatic compound |
| JPS59218157A (en)* | 1983-05-20 | 1984-12-08 | バックスター インターナショナル インコーポレーテッド | Production of anti-bacterial catheter |
| JPS63145660A (en)* | 1986-09-05 | 1988-06-17 | アメリカン・サイアナミド・カンパニー | Coating of surgical filament |
| JPS6468478A (en)* | 1987-09-07 | 1989-03-14 | Agency Ind Science Techn | Metal plating method using silver hydrosol |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246661A (en)* | 2001-02-20 | 2002-08-30 | Toshiba Corp | Thermoelectric processing system |
| JP2013544972A (en)* | 2010-11-26 | 2013-12-19 | シー・アール・バード・インコーポレーテッド | Deposition of silver layer on non-conductive substrate |
| Publication number | Publication date |
|---|---|
| AU5473490A (en) | 1990-11-08 |
| DK0400349T3 (en) | 1996-03-18 |
| ATE134719T1 (en) | 1996-03-15 |
| ES2086328T3 (en) | 1996-07-01 |
| FI95816B (en) | 1995-12-15 |
| CA2016081A1 (en) | 1990-11-04 |
| NO901974L (en) | 1990-11-05 |
| JPH08325743A (en) | 1996-12-10 |
| JP2645431B2 (en) | 1997-08-25 |
| EP0693576A1 (en) | 1996-01-24 |
| EP0400349A1 (en) | 1990-12-05 |
| US5395651A (en) | 1995-03-07 |
| FI902219A0 (en) | 1990-05-03 |
| US6224983B1 (en) | 2001-05-01 |
| DE69025495D1 (en) | 1996-04-04 |
| JPH08333687A (en) | 1996-12-17 |
| AU642872B2 (en) | 1993-11-04 |
| CA2016081C (en) | 1999-04-06 |
| EP1375700A1 (en) | 2004-01-02 |
| FI95816C (en) | 1996-03-25 |
| NO304746B1 (en) | 1999-02-08 |
| GR3019899T3 (en) | 1996-08-31 |
| US5747178A (en) | 1998-05-05 |
| NO901974D0 (en) | 1990-05-03 |
| US5965204A (en) | 1999-10-12 |
| EP0400349B1 (en) | 1996-02-28 |
| JP3030687B2 (en) | 2000-04-10 |
| DE69025495T2 (en) | 1996-07-11 |
| Publication | Publication Date | Title |
|---|---|---|
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